1. Field of the Invention
The present invention relates to new selective hydrogenation catalysts and the method of making the catalysts, which are useful for hydrogenation, such as selective hydrogenation of acetylenic impurities in crude olefin and diolefin streams. In particular the invention relates to nickel-based catalysts.
2. Related Information
In the manufacture of olefins such as ethylene, propylene, butadiene, isoprene, etc., acetylenic impurities such as acetylene, methyl acetylene, vinyl acetylene, ethyl acetylene, 2-methyl-1-buten-3-yne, etc. in various crude mixed C2-C5 streams need to be removed with a minimum loss of useful materials such as ethylene, propylene, butenes, butadiene, isoprene, etc. in the feed streams.
1,3-butadiene is an important raw material used to produce various polymers such as butadiene-styrene copolymer. One of the processes for producing 1,3-butadiene is co-production of various olefins by steam cracking of petroleum fractions. The crude mixed C4 stream from a steam cracker is selectively hydrogenated to partially remove C4 acetylenic compounds. The selectively hydrogenated stream is sent to the 1,3-butadiene recovery unit where solvent extractive distillation techniques are used to separate 1,3-butadiene from the rest of components in the mixed stream. Solvent extractive distillation is expensive to operate and energy consumption is intensive.
Complete removal of C4 acetylenic compounds in the stream with high recovery of 1,3-butadiene is highly desirable to reduce the production cost of 1,3-butadiene and produce a premium quality product for polymer production. However, formerly it was technically impossible to completely remove C4 acetylenes in crude mixed streams by selective hydrogenation without unacceptably high loss of 1,3-butadiene due to over-hydrogenation of 1,3-butadiene. Therefore, an improved inexpensive process via a highly active and selective catalyst is highly desirable to produce premium quality 1,3-butadiene without paying a penalty for high loss of 1,3-butadiene due to over-hydrogenation.
The preferred technique for the purification in commercial practice is the selective hydrogenation of acetylenic compounds over hydrogenation catalysts. Supported Pd, Ni, Cu and Co catalysts are known as useful for the hydrogenation of acetylenes (Handbook of Commercial Catalysts, pp. 105-138, Howard F. Rase, CRC Press, 2000). The most preferred catalysts in prior commercial applications of selective hydrogenation of acetylenes are palladium-based catalysts such as Pd, Pd/Pb, Pd/Ag or Pd/Au on a support such as alumina and the copper catalysts on a support such as alumina. Pd catalysts were the most preferred catalysts because of high activity and supposedly superior selectivity compared with other metal catalysts.
Palladium-based catalysts are not selective enough to completely remove C4 acetylenes without an unacceptable amount of 1,3-butadiene loss due to over-hydrogenation. Another inherent problem of palladium-based catalysts is the loss and migration of palladium due to the formation of soluble Pd complex compounds by the reaction of Pd atoms on the catalyst surface with vinyl acetylene, if the hydrogenation is carried out in the presence of liquid phase. Silver and gold have been used to minimize the loss of palladium and reduce catalytic polymerization of acetylenic compounds.
The copper-based catalysts are very selective so that the recovery of 1,3-butadiene from the mixed stream is very high compared with palladium-base catalysts. However, since the activity of copper catalysts is very low compared with palladium-based catalysts, a large volume of catalyst and large reactor are required. Also because of deposition of heavy carbonaceous materials on the catalyst is relatively fast, frequent regeneration of catalysts necessitates multiple reactors.
Ni catalysts in any form are very active catalysts for selective hydrogenation of acetylenes and dienes. According to R. S. Mann et al. (Can. J. Chem. 46, p. 623, 1968), Ni and Ni—Cu alloy catalysts are effective for methyl acetylene hydrogenation. The catalytic activity rapidly increases with addition of copper to nickel up to 25 wt. % in alloy catalyst. The selectivity to propylene and extent of polymerization increase with the increase of copper in the alloy. According to H. Gutmann and H. Lindlar (Organic Synthesis, Chapter 6), vinyl acetylene and 2-methyl-1-buten-3-yne are difficult to selectively hydrogenate to 1,3-butadiene and isoprene by using the usual palladium, nickel or cobalt catalysts. Nickel-based catalysts have been used in commercial processes for the selective hydrogenation of acetylenic impurities in mixed steams of olefins and diolefins.